Printing cellulosic textile materials



Patented Feb. 10, 1942 UNITED STATES PRINTING CELLULO SIC TEXTILE MATERIALS Denys Percival Milburn, Bombay, India, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application September 10, 1940, Serial No. 356,209. In Great Britain March 10,

9 Claims.

The present invention relates to the printing of cellulosic textile fabrics in resist styles so that there are produced white patterns on a coloured ground or, alternatively, coloured patterns on a differently coloured ground.

This application is a continuation-in-part of my copending application, Serial Number 194,703, filed March 8, 1938, which became U. S. Patent No. 2,217,805 on October 15, 1940.

It is known to produce resists, either white or illuminated with azoic dyestuffs on a ground dyed with an ester salt of a leuco vat dyestuff by incorporated in the printing paste a quaternary ammonium salt. However, the known processes contemplate only the use of quaternary ammonium salts in which either the only aliphatic substituents present on the quaternary nitrogen atom are methyl groups or, where long chain alkyl groups are present, these are attached directly to the quaternary nitrogen atom. These salts act insofar as at the printed places of the fabric the ester salt forms with the quaternary ammonium salt there present a precipitate of a sparingly soluble compound which is resistant to alkali and does not dye the fibre. The subsequent removal from the fibre of this pre cipitate, which is of a tarry nature, necessitates an unusually severe soaping treatment, which calls for abnormally frequent emptying and resetting of the soap becks.

It was not to be foreseen that by the process of the present invention, which comprises incorporating in the printing paste a quaternary ammonium salt in which a long chain aliphatic hydrocarbon radical is attached not directly to the quaternary nitrogen atom, but through a particular bridging group, there would be imparted to the fabric, in the printed areas, temporary water-repellent properties, such that the ester salts does not come into contact with the fibre in those areas. It will be appreciated that the use of such compounds simplifies the subsequent processing of the fabric since a clean resist is thereby produced without the simultaneous deposition on the fibre of an insoluble tarry substance, the subsequent removal of which demands unusually severe soaping treatments.

According to the invention cellulosic textile materials are printed with a printing paste containing, besides other usual ingredients, a compound of the general formula wherein R is a long-chain aliphatic radical, having not less than 11 carbon atoms, which radical maybe saturated or unsaturated hydrocarbon radical; (in other words, RCO is the radical of a long chain carboxylic acid, i. e. of What is commonly known as a fatty acid in the original etymological sense) X stands for hydrogen or a hydrocarbon radical exemplified by alkyl radicals, such as methyl, ethyl, etc., aralkyl groups, such as benzyl, and aryl groups, such as phenyl; the group N (tert) may represent the residue of a tertiary aliphatic base, or may stand for the residue of a heterocyclic base, such as pyridine or quinoline; finally, the symbol Y stands for the monovalent anion of an acid, for instance, of hydrochloric, hydrobromic, nitric, sulphuric, ptoluene sulphonic, oxalic, and the like; the soprinted material is then dried and heated as by steaming for a short time and is then dyed, conveniently by padding; finally, the ground colour having been developed if necessary, the material is washed, soaped and dried in the usual way.

It will be understood that when the printing paste contains only the resisting agent, together with the usual thickeners, for example, gum senegal, gum tragacanth or British gum, and assistants, for example, emulsifying agents, such as sulphated fatty alcohols, there are produced, finally, white patterns on a coloured ground.

Alternatively the printing paste may contain, in addition to the resist agent and other ingredients, an ice colour preparation which is capable of being developed by treatment with acid. In this case, the steaming operation to which, after printing and drying, the fabric is subjected, is modified in that it is carried out in the presence of the vapour of a suitable acid, for example, formic acid or acetic acid. In this Way there are finally produced coloured patterns on a differently coloured ground.

As dyestuffs for providing the ground colour, which is preferably applied by padding, I may use vat dyestuffs (applied either as such from reduction medium or in the soluble leuco ester form), azoic colours (applied, for instance, as ready-for-printing preparations of e. g. diazoimino compound and coupling component) or mordant dyestuffs.

In carrying the invention into practical effect it is preferable to work as far as possible at low temperatures (e. g. room temperature), as by using cold padding liquors and drying the fabric after padding by means of hot air rather than by passing it over heated cylinders. It is believed that the success of the process depends upon the production, during the steaming operation, of temporarily water-repellent areas on the fabric Where the printing paste has been applied. Such water-repellency Would be impaired or destroyed by working at elevated temperatures.

Padding is preferably done through the nip so as to minimise the time of contact of the fabric with the padding liquor.

As suitable compounds of formula If desired, the said quaternary ammonium salts may be used in conjunction with other known resist agents, for example gelatine, glue size, or other proteins or albumenoids. It has been found that printing pastes which contain an ice color preparation that can be developed with acid and stearmidomethylpyridinium chloride can be improved and used with a greater margin of safety if there is added to the printing paste a small amount of a supplementary resist agent, such as benzyl trimethyl ammonium hydroxide. The addition of about 4% of a 40% aqueous solution of benzyl trimethyl ammonium hydroxide to prin ing pastes which do not contain this supplementary resist agent has been found advantageous.

As thickening agents there may be used, for example, British gum, starch-British gum, gum Senegal, gum Arabic or gum tragacanth.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 Cotton fabric is printed with a paste made by incorporating together:

Parts Stearamidomethylpyridinium chloride 4 Diacetone alcohol 5 Starch-tragacanth thickening 1:1 50 Water 41 In making up this paste the temperature should preferably not be allowed to exceed 40 C.

The printed fabric is dried, steamed for minutes, and then grounded in one of the following solutions:

Soledon Jade Green XS paste (the sulphuric ester of leuco dimethoxydibenzanthrone) l 3 Soledon Orange RS powder (Schultz Farbstofltabcllen, 7th edition No. 1349) through a 2% solution of sulphuric acid (168 Tw.) at 70 C., washed, soaped and dried. There is thus obtained a clear-cut white pattern on a green or an orange ground.

Example 2 Cotton fabric is printed and steamed as in Example 1. It is then grounded by padding in one of the following solutions:

Caledon Jade Green paste (Colour Index No. 1101). Caledon Blue 3G paste (Colour Index No. 1109). Tragacanth thickening 1:1 Sodium formaldehyde sulphoxylate. Potassium carbonate The grounded print is dried, steamed for 10 minutes, oxidised in the usual manner to develop the ground colour, soaped at the boil and again dried. There is thus obtained a clear-cut white pattern on a green or a blue ground.

Example 3 acid (Colour Index No. 722) l Acetate of chrome liquor 28 Tw 7 Tragacanth thickening 1:1 5 Water 87 The grounded print is steamed for /2-1'10111', washed, soaped and dried. There is thus obtained a clear-cut white pattern on a blue ground.

Example 4 Cotton fabric is printed and steamed as in Example 1 and then padded with one of the following solutions:

An azoic dyestutI printing preparation as commercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-chloro-otoluidine and the o-toluididc of 2:3-hydroxynaphthoic acid 0. 7

An azoic dyestufi printing preparation as commercially supplied. comprising a diazoimino compound from diazotised 4-benzoylamino-2z5- diethoxy-aniline mixed with the anilide oi 2:3-

hydroxynapht'hoic acid l Caustic soda aqueous solution 76: 'lw l 2 Tragacanth thickening 1:1 5 5 Water 93. 3 92 It is then dried, steamed for 15 minutes in the presence of acetic and formic acid vapours, washed, soaped at the boil and dried. There is thus obtained a clear-cut white pattern on a red or a blue ground.

Example 5 The following mixtures P and Q are made up separately by warming the ingredients together until all is dissolved, (the temperature not exceeding 40 C. in the case of Q) Parts An azoic dyestufi printing preparation as commercially supplied comprising a mixture of a diazoimino compound of diazotized 4-chloro-o-toluidine and the P -toluidide of 2:3-hydr0xynaphthoic acid '7 Methylated spirit 3 Aqueous sodium hydroxide 76 Tw 3 Starch-tragacanth thickening (1:1) 30 Water Stearamidomethylpyridinium chloride 4 Diacetone alcohol 5 Q Starch-tragaoanth thickening 1:1) Water 18 P and Q are then cooled and mixed together to form a printing paste. Cotton fabric is printed with the printing paste so made, dried and steamed in the presence of acetic and formic acid vapours for A; to -hour. The printed fabric is then grounded by padding in one of the following liquors Soledon Jade Green XS paste (=sulphuric ester of leuco dimethoxydibenzanthrone) A blue dyestufl which is the sulphuric ester of leuco 16:17-diethylene ether of dihydroxydibenzanthrone in the form of a 20%aqueous paste Tragacanth thickening (l: l) Sodium nitrite aqueous solution Water The fabric is then dried, preferably by hot air, and developed by passage through a 2% aqueous solution of sulphuric acid (168 Tw.) at 70 C. Finally it is washed, soaped at the boil and dried. There is obtained a clear-cut red pattern on a green or a blue ground.

Example 6 Cellulosic fabric is printed and steamed as in Example 5. It is then grounded by padding in the following liquor:

. Parts An azoic dyestuif printing preparation, as

commercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-benzoylamino-2 5-diethoxy-aniline, and the anilide of 2:3-hydroxynaphthoic a id 2 Aqueous sodium hydroxide 76 Tw 3 Tragacanth thickening (1:1) 5 Water 90 It is then dried and steamed in the presence of acetic and formic acid vapours for A; to /2-hour and finally soaped at the boil and dried. There is thus obtained a clear-cut red pattern on a blue ground.

Example 7 Cellulosic fabric is printed and steamed as in Example 5. It is then grounded by padding in the following liquor:

Parts A blue dyestuff which is the sodium salt of L-sulphohydroxydimethylfuchson dicarboxylic acid 1 Aqueous acetate of chrome solution 28 Tw 7 Tragacanth thickening (1:1) 5 Water 8'7 The printed and grounded fabric is then steamed for V2 to 1 hour, soaped and dried. There is thus obtained a clear-cut red pattern on a blue-violet ground.

Earample 8 Stearamidomethylpyridinium chloride Q Beta-ethoxyethanol;

Starch-tragacanth thickening (1:1) 20 Water 21-18 ,L H00 01 OOWOOR'I P and Q are then cooled and mixed to form a printing paste. Cotton fabric is printed with the printing paste so made, dried and steamed in the presence of acetic and formic acid vapours for 15 minutes. The printed fabric is then grounded by padding in the following liquor:

Parts Fast Printing Green S (Colour Index No. 2) 2 Water 89 Tragacanth thickening (1:1) 5 Aqueous ferrous sulphate 21 Tw 4 The printed and grounded fabric is then dried and passed through a boiling 1% aqueous solution of sodium carbonate (anhydrous), washed, soaped at the boil and dried. There is thus obtained a clear-cut scarlet pattern on a green ground.

Example 9 Cotton fabric is printed and steamed as in Example 5. It is then grounded by padding with the following liquor:

Parts Caledon Jade Green X 200 paste fine (Colour Index No. 1101) 2 Aqueous caustic soda 76 Tw 2 Sodium hydrosulphite 2 Water 94 In making up this solution the first three ingredients are heated with 30 parts of Water until the dyestufi is completely vatted; the solution is then cooled and the remaining 64 parts of Water are added.

After padding, the material is exposed to the air for /2-minute to develop the ground colour and then washed, chromed, soaped at the boil and dried. There is obtained a clear cut red pattern on a green ground.

The above examples deal only with the application of the process to cotton fabric, but it is to be understood that it can be applied also to other cellulosic material, e. g. viscose rayon and also to fabrics constituted in part of other textile fibres, for example certain cotton-wool, viscosewool or viscose-pure silk unions.

I claim:

1. A process of printing cellulosic textile materials in resist styles to produce patterns on a colored ground which comprises applying to the cellulosic textile material a resist printing paste which contains as the active resist agent a compound of the general formula wherein R stands for a long chain aliphatic radical containing at least 11 carbon atoms, X is a member of the group consisting of hydrogen and hydrocarbon radicals, N (tert) represents the entire molecular structure of a tertiary amine selected from the group consisting of tertiary aliphatic amines and tertiary heterocyclic bases, and Y stands for the monovalent anion of an acid, steaming the material, and then dyeing it to produce a ground shade.

2. A process as claimed in claim 1 wherein the printing paste also contains an ice color preparation capable of being developed by acid.

3. A process as claimed in claim 1 wherein the dyestuff which is used to produce the ground shade is applied by padding.

4. A process of coloring cellulosi-c fabric in predetermined designs which comprises printing upon the same in predetermined designs a resist printing paste comprising as active resist a compound of the general formula wherein R stands for a long chain aliphatic hydrocarbon radical containing at least 11 carbon atoms, N(tert) represents the entire molecular structure of a tertiary amine selected from the group consisting of tertiary aliphatic amines and tertiary heterocyclic bases, and Y stands for the monovalent anion of an acid, drying the printed fabric, steaming the dried fabric to develop a temporary water-repellent effect in the printed areas, then padding the fabric with a developable ground color, and further treating the same to develop the ground color.

5. A process of printing cellulosic textile materials in resist styles to produce patterns on a colored ground which comprises applying to the cellulosic textile material a resist printing paste which contains as the active resist agent a compound having the general formula wherein R stands for a long chain aliphatic hydrocarbon radical containing at least 11 carbon atoms, N(tert) represents the entire molecular structure of a tertiary heterocyclic amine, and Y stands for the monovalent anion of an acid, drying the material, steaming the material to develop a temporary water-repellent effect in the printed areas, and then padding the material with the dyestulf which is employed to produce the ground shade.

6. A process of printing cellulosic textile materials in resist styles to produce colored patterns on a differently colored ground which comprises applylng to the cellulosic textile material a resist printing paste containing an ice color preparation capable of being developed by acid and as the active resist agent a compound of the general formula wherein R stands for a long chain aliphatic hydrocarbon radical containing at least 11 carbon atoms, N(tert) represents the entire molecular structure of a tertiary amine selected from the group consisting of tertiary aliphatic amines and tertiary heterocyclic bases, and Y stands for the monovalent anion of an acid, drying the printed fabric, steaming the dried fabric in the presence of acid vapors to develop both the color and a temporary water-repellent effect in the printed areas, and then padding the material with the dyestuif which is employed to produce the ground shade.

7. A process of printing cellulosic textile materials in resist styles to produce patterns on a colored ground which comprises applying to the cellulosic textile material a resist printing paste which contains as the active resist agent a compound having the general formula wherein R stands for a long chain aliphatic hydrocarbon radical containing at least 11 carbon atoms, NC5H5 represents the entire molecular structure of pyridine, and Y stands for the monovalent anion of an acid, drying the material, steaming the material to develop a temporary Water-repellent elTect in the printed areas, and then padding the material with the dyestuff which is employed to produce the ground shade.

8. A process as set forth in claim 7 wherein a stearamidomethylpyridinium salt is used as the active resist agent in the resist printing paste.

9. A process as set forth in claim '7 wherein stearamidomethylpyridinium chloride is used as the active resist agent in the resist printing paste.

DENYS PERCIVAL MILBURN. 

